RESUMEN
A novel and convenient protocol for the catalytic hydrogen-deuterium exchange of biologically active tertiary amines utilizing the borrowing hydrogen methodology has been developed. In the presence of the readily available Shvo catalyst, excellent chemoselectivity toward α- and ß-protons with respect to the nitrogen atom as well as high degree of deuterium incorporation and functional group tolerance is achieved. This allowed for the deuteration of complex pharmaceutically interesting substrates, including examples for actual marketed drug compounds. Notably, this method constitutes a powerful tool for the generation of valuable internal standard materials for LC-MS/MS analyses highly demanded for various life-science applications.
Asunto(s)
Aminas/química , Deuterio/química , Rutenio/química , Catálisis , Medición de Intercambio de Deuterio , Hidrógeno/química , Preparaciones Farmacéuticas/química , Espectrometría de Masas en TándemRESUMEN
Amid(e) them all: primary carboxamides and ureas react with aromatic and aliphatic amines in the presence of a copper catalyst to give a wide range of functionalized amides.
Asunto(s)
Amidas/química , Aminas/química , Cobre/química , Urea/química , Aminación , Catálisis , EstereoisomerismoRESUMEN
Highly selective alkyl transfer processes of mono-, di- and trialkyl amines in the presence of the Shvo catalyst have been realized; in addition, a general method for N-alkylation of aniline with di- and trialkyl amines is presented.
Asunto(s)
Aminas/química , Compuestos de Anilina/química , Remoción de Radical Alquila , Especificidad por SustratoAsunto(s)
Aminas/síntesis química , Amoníaco/química , Rutenio/química , Aminación , Aminas/química , Catálisis , Hidrogenación , Estructura MolecularAsunto(s)
Alcoholes/química , Aminas/síntesis química , Amoníaco/química , Rutenio/química , CatálisisRESUMEN
The monoamination of vicinal diols in the presence of in situ generated ruthenium catalysts has been investigated. Among the various phosphines tested in combination with [Ru(3)(CO)(12)], N-phenyl-2-(dicyclohexyl-phosphanyl)pyrrole showed the best performance. After optimization of the reaction conditions this system was applied to different secondary amines and anilines as well as a number of vicinal diols. With the exception of ethylene glycol, monoamination of the vicinal diols occurred selectively and the corresponding amino alcohols were obtained in good yields, producing water as the only side product.